U.S. patent application number 16/320606 was filed with the patent office on 2019-05-23 for epoxy (meth) acrylate compound and curable composition containing same.
This patent application is currently assigned to SHOWA DENKO K. K.. The applicant listed for this patent is SHOWA DENKO K. K.. Invention is credited to Jun DOU, Yoshitaka ISHIBASHI, Masahiko TOBA, Hiroshi UCHIDA, Chika YAMASHITA.
Application Number | 20190153149 16/320606 |
Document ID | / |
Family ID | 61016309 |
Filed Date | 2019-05-23 |
View All Diagrams
United States Patent
Application |
20190153149 |
Kind Code |
A1 |
TOBA; Masahiko ; et
al. |
May 23, 2019 |
EPOXY (METH) ACRYLATE COMPOUND AND CURABLE COMPOSITION CONTAINING
SAME
Abstract
[Problem] To provide an epoxy (meth)acrylate compound that
serves as a material for a protective film that is unlikely to
cause migration to an electrically conductive pattern, and a
curable composition containing the epoxy (meth)acrylate compound.
[Solution] Provided is an epoxy (meth)acrylate compound which is
characterized by being represented by general formula (1) and in
which the content of halogen atoms, which are impurities, is 100
ppm by mass or less. In addition, provided is a curable composition
for forming a protective film for an electrically conductive
pattern, the curable composition being obtained by mixing this
epoxy (meth)acrylate compound with a photopolymerization initiator
and at least one type of monomer or oligomer that contains a
(meth)acryloyl group. ##STR00001## (At least one of R.sup.1 to
R.sup.5 has a structure represented by formula (2), and the
remainder of R.sup.1 to R.sup.5 are each independently selected
from the group consisting of hydrogen atoms and alkyl groups and
alkoxy groups having 1-6 carbon atoms. R.sup.6 denotes a hydrogen
atom or a methyl group.) ##STR00002## (* denotes the bonding
position to a carbon atom that constitutes the benzene ring to
which R.sup.1 to R.sup.5 are bonded in formula (1), and R.sup.7
denotes a hydrogen atom or a methyl group.)
Inventors: |
TOBA; Masahiko; (Tokyo,
JP) ; DOU; Jun; (Tokyo, JP) ; YAMASHITA;
Chika; (Tokyo, JP) ; ISHIBASHI; Yoshitaka;
(Tokyo, JP) ; UCHIDA; Hiroshi; (Tokyo,
JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SHOWA DENKO K. K. |
Tokyo |
|
JP |
|
|
Assignee: |
SHOWA DENKO K. K.
Tokyo
JP
|
Family ID: |
61016309 |
Appl. No.: |
16/320606 |
Filed: |
July 24, 2017 |
PCT Filed: |
July 24, 2017 |
PCT NO: |
PCT/JP2017/026644 |
371 Date: |
January 25, 2019 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08F 222/1006 20130101;
C08F 299/02 20130101; C08G 59/027 20130101; C08L 63/10 20130101;
C08F 290/061 20130101; C08G 59/1466 20130101; C08G 59/022 20130101;
C08F 20/32 20130101; C08G 59/245 20130101; C08F 290/061 20130101;
C08F 222/1006 20130101 |
International
Class: |
C08G 59/17 20060101
C08G059/17; C08G 59/02 20060101 C08G059/02; C08G 59/24 20060101
C08G059/24 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 28, 2016 |
JP |
2016-148390 |
Claims
1. An epoxy (meth)acrylate compound represented by Formula (1), and
having a halogen atom content of 100 ppm by mass or less:
##STR00021## (wherein, at least one of R.sup.1 to R.sup.5 has a
structure represented by Formula (2); the remainders of R.sup.1 to
R.sup.5 are each independently selected from a group consisting of
a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an
alkoxy group having 1 to 6 carbon atoms; and R.sup.6 represents a
hydrogen atom or a methyl group), ##STR00022## (wherein, *
represents a bonding position to a carbon atom that constitutes the
benzene ring to which R.sup.1 to R.sup.5 are bonded in Formula (1);
and R.sup.7 represents a hydrogen atom or a methyl group).
2. An epoxy (meth)acrylate compound according claim 1, wherein the
epoxy (meth)acrylate compound is a compound represented by Formula
(3) or Formula (4): ##STR00023## (wherein, R.sup.8 represents a
hydrogen atom or a methyl group), ##STR00024## (wherein, R.sup.9
represents a hydrogen atom or a methyl group).
3. A curable composition comprising: an epoxy (meth)acrylate
compound according to claim 1, at least one of monomers and
oligomers containing a (meth)acryloyl group, and a
photopolymerization initiator.
4. A curable composition comprising: an epoxy (meth)acrylate
compound according to claim 2, at least one of monomers and
oligomers containing a (meth)acryloyl group, and a
photopolymerization initiator.
Description
TECHNICAL FIELD
[0001] The present disclosure relates to an epoxy (meth)acrylate
compound and a curable composition containing the same.
BACKGROUND ART
[0002] In a case such that a conductive pattern formed on a
substrate has a very small thickness, a technology to form an
insulative thin film which protects the conductive pattern, may be
required. As a material for such an insulative thin film, for
example, the below-mentioned Patent Document 1 discloses an epoxy
acrylate resin, and the Patent Document 2 discloses a feature of
adding a gallic acid or propyl gallate to an acrylic resin-based
binder (polymer, monomer, or oligomer).
PRIOR ARTS
[0003] Patent Document [0004] Patent Document 1: Japanese
Unexamined Patent Publication (Kokai) No. H7-48424 [0005] Patent
Document 2: Japanese Unexamined Patent Publication (Kokai) No.
2014-191894
SUMMARY
[0006] However, the epoxy acrylate resin disclosed in Patent
Document 1 is synthesized using an epoxy resin which is synthesized
by ring-opening polymerization of epichlorohydrin. Further,
triethyl-benzylammonium chloride is used for forming the epoxy
acrylate resin. Therefore, some chlorine remains in the epoxy
acrylate resin, which leads to a drawback that migration easily
occurs in the conductive pattern.
[0007] With respect to the protective film using a gallic acid or
propyl gallate, which is disclosed in Patent Document 2, the
inventors of Patent Document 2 prepare a transparent conductive
film by coating aqueous dispersion containing synthesized silver
nanowires on an easily adhesive surface of a high-transparency PET
film, and by drying and pressurizing the resultant; and prepare a
conductive layer by forming a protective layer on the obtained
transparent conductive film. According to the reliability test of
the conductive layers, after the conductive layers were left for
500 hours under the conditions of 85.degree. C. and 85% relative
humidity, sheet resistance increase rates of a large number of
conductive layers each having the protective layer formed thereon
are 20% or more and less than 30% (refer to Table 1). Therefore,
deterioration of the conductive pattern, migration at the time of
electric field application, etc., are suspected.
[0008] One of the objectives of the present disclosure is to
provide an epoxy (meth)acrylate compound that serves as a material
for a protective film that is unlikely to cause migration in a
conductive pattern, and a curable composition containing the epoxy
(meth)acrylate compound.
[0009] The present disclosure includes the following aspects.
[0010] [1] An epoxy (meth)acrylate compound represented by Formula
(1), and having a halogen atom content of 100 ppm by mass or
less:
##STR00003##
[0011] (wherein, at least one of R.sup.1 to R.sup.5 has a structure
represented by Formula (2); the remainders of R.sup.1 to R.sup.5
are each independently selected from a group consisting of a
hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an
alkoxy group having 1 to 6 carbon atoms; and R.sup.6 represents a
hydrogen atom or a methyl group),
##STR00004##
[0012] (wherein, * represents a bonding position to a carbon atom
that constitutes the benzene ring to which R.sup.1 to R.sup.5 are
bonded in Formula (1); and R.sup.7 represents a hydrogen atom or a
methyl group).
[0013] [2] An epoxy (meth)acrylate compound according to above [1],
wherein the epoxy (meth)acrylate compound is a compound represented
by Formula (3) or Formula (4):
##STR00005##
[0014] (wherein, R.sup.8 represents a hydrogen atom or a methyl
group),
##STR00006##
[0015] (wherein, R.sup.9 represents a hydrogen atom or a methyl
group).
[0016] [3] A curable composition comprising: an epoxy
(meth)acrylate compound according to above [1] or [2], at least one
of monomers and oligomers containing a (meth)acryloyl group, and a
photopolymerization initiator.
[0017] According to the present disclosure, an epoxy (meth)acrylate
compound that serves as a material for a protective film that is
unlikely to cause migration in a conductive pattern, and an ink
composition containing the epoxy (meth)acrylate compound, can be
provided.
BRIEF DESCRIPTION OF DRAWINGS
[0018] FIG. 1 shows a .sup.1H-NMR spectrum of an eugenol-derived
epoxide synthesized according to Synthesis Example 1.
[0019] FIG. 2 shows a .sup.1H-NMR spectrum of a
2-allylphenol-derived epoxide synthesized according to Synthesis
Example 2.
[0020] FIG. 3 shows a .sup.1H-NMR spectrum of an eugenol-derived
epoxy acrylate according to Example 1.
[0021] FIG. 4 shows a .sup.1H-NMR spectrum of a
2-allylphenol-derived epoxy acrylate according to Example 2.
ASPECT OF DISCLOSURE
[0022] Hereinbelow, an aspect of the present disclosure
(hereinbelow, referred to as an aspect) will be explained. In the
present specification, a (meth)acrylate refers to an acrylate or a
methacrylate, a (meth)acrylic acid refers to an acrylic acid or a
methacrylic acid, and a (meth)acryloyl group refers to an acryloyl
group or a methacryloyl group, respectively.
Epoxy (Meth)Acrylate Compound
[0023] An epoxy (meth)acrylate compound according to an aspect is
characterized in: having a structure in which a plurality of epoxy
groups bonded to a benzene ring through a carbon atom, or a carbon
atom and an oxygen atom, are bonded to a carboxyl group of a
(meth)acrylic acid; and having a halogen atom content of 100 ppm by
mass or less. The plurality of epoxy groups are bonded to one
benzene ring through a carbon atom, or a carbon atom and an oxygen
atom.
[0024] The epoxy (meth)acrylate compound may be represented by the
following general formula.
##STR00007##
[0025] (wherein, at least one of R.sup.1 to R.sup.5 has a structure
represented by Formula (2); the remainders of R.sup.1 to R.sup.5
are each independently selected from a group consisting of a
hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an
alkoxy group having 1 to 6 carbon atoms; and R.sup.6 represents a
hydrogen atom or a methyl group).
##STR00008##
[0026] (wherein, * represents a bonding position to a carbon atom
that constitutes the benzene ring to which R.sup.1 to R.sup.5 are
bonded in Formula (1); and R.sup.7 represents a hydrogen atom or a
methyl group).
[0027] Preferable examples of the alkyl group and alkoxy group
having 1 to 6 carbon atoms may include a methyl group, an ethyl
group, an isopropyl group, a t-butyl group, a methoxy group, an
ethoxy group, an isopropoxy group, a t-butoxy group, and the like.
A specific example of the epoxy (meth)acrylate compound may be an
eugenol-derived epoxy (meth)acrylate having the following
structure.
##STR00009##
[0028] (wherein, R.sup.8 represents a hydrogen atom or a methyl
group).
[0029] Further, another specific example may be a
2-allylphenol-derived epoxy (meth)acrylate having the following
structure.
##STR00010##
[0030] (wherein, R.sup.9 represents a hydrogen atom or a methyl
group).
[0031] In the present specification, each of the terms
eugenol-derived and 2-allylphenol-derived refers to a starting
material for synthesizing a corresponding epoxy compound, the
starting material being a compound having a hydroxy group (alcohol
or phenol).
[0032] The above-mentioned eugenol- or 2-allylphenol-derived
epoxide is preferable as a compound that serves as a raw material,
the compound having epoxy groups bonded to a benzene ring through a
carbon atom, or a carbon atom and an oxygen atom. Both eugenol and
2-allylphenol are offered commercially and easily available.
Further, the eugenol and 2-allylphenol each includes one allyl
group bonded to a benzene ring, in a molecule, and thus, when
another allyl group is further introduced, using the easily
ignitable palladium carbon (Pd/C), as a catalyst, the use amount of
the palladium carbon (Pd/C) can be reduced. By using such materials
having a low epoxy equivalent, epoxy (meth)acrylate having a high
acrylate functional group concentration can be produced, and a
degree of crosslinkage of the cured coated film can be designed
high. In addition, because the material contains a benzene ring,
thanks to the n-interaction with an aromatic ring, an adhesion
property to a substrate containing an aromatic ring, such as PET
(polyethylene terephthalate), PEN (polyethylene naphthalate), PI
(polyimide), etc., can be increased.
[0033] Preferably, the eugenol-derived epoxide or the
2-allylphenol-derived epoxide may be prepared by epoxidizing, with
hydrogen peroxide, a carbon-carbon double bond constituting an
allyl group in the allyl ether of the raw material, i.e., eugenol
or 2-allylphenol, and thereby, a halogen-free epoxy compound can be
obtained.
[0034] The eugenol-derived epoxide may be produced by the reaction
represented by the following Formula (5), using, for example, an
allyl ether compound of eugenol, as a raw material.
##STR00011##
[0035] Also, the 2-allylphenol-derived epoxide may be produced by
the reaction represented by the following Formula (6), using, for
example, an allyl ether compound of 2-allylphenol, as a raw
material.
##STR00012##
[0036] As a source for hydrogen peroxide, a hydrogen peroxide
aqueous solution is preferable. The concentration of the hydrogen
peroxide aqueous solution is not limited, but in general,
preferably 1 to 60% by mass, more preferably 5 to 50% by mass, and
still more preferably 10 to 40% by mass. The concentration of 1% by
mass or more is preferable from the viewpoint of industrial
productivity, and from the viewpoint of energy-cost at the time of
separation. The concentration of 60% by mass or less is preferable
from the viewpoints of economy and safety.
[0037] The amount of hydrogen peroxide usage is not particularly
limited. As the reaction progresses, the hydrogen peroxide is
consumed. Thus, maintaining the concentration in the reaction
system by continuously adding and replenishing hydrogen peroxide,
is desirable. The concentration of the hydrogen peroxide present in
the reaction system is maintained preferably 0.01 to 0.5 molar
equivalent, more preferably 0.02 to 0.2 molar equivalent, and still
more preferably 0.05 to 0.1 molar equivalent, relative to the
carbon-carbon double bonds in the allyl ether compound of the raw
material. If the concentration of the hydrogen peroxide present in
the reaction system is 0.01 molar equivalent or more, relative to
the carbon-carbon double bonds in the allyl ether compound of the
raw material, productivity is preferable. If the concentration is
0.5 molar equivalent or less, a sufficient safety can be ensured
even in a mixed composition of a solvent and water. At the early
stage of the reaction, if a large amount of hydrogen peroxide is
supplied in the reaction system at a time, the reaction may
progress too rapidly, leading to a dangerous situation. Therefore,
as mentioned below, adding the hydrogen peroxide slowly is
preferable. The hydrogen peroxide concentration in the reaction
system at the end of the reaction is not limited, and the
concentration of the hydrogen peroxide present in the reaction
system may be 0.01 molar equivalent or less, relative to the
concentration of the carbon-carbon double bonds in the allyl ether
compound of the raw material.
[0038] In the above reaction, acetonitrile is used for epoxidizing
the allyl group, with hydrogen peroxide, in coexistence with base.
The hydrogen peroxide acts on acetonitrile, and a peroxy imidic
acid which is active on the oxidation reaction is formed. The
oxidation reaction progresses with the peroxy imidic acid serving
as reaction active species. According to this method, the reaction
can be performed under the neutral or basic condition. Therefore,
the method has broad utility, and is advantageous in cost because
the use of special test reagent is not required.
[0039] The amount of acetonitrile provided at the start of the
reaction is preferably, in terms of nitrile group, 2.0 to 15 molar
equivalent, more preferably 3.0 to 10 molar equivalent, and still
more preferably 4.0 to 8.0 molar equivalent, relative to the
carbon-carbon double bonds in the allyl ether compound of the raw
material. Although depending on the structure of the allyl ether
compound of the raw material, if the amount of acetonitrile used is
2 to 15 molar equivalent, in terms of nitrile group in
acetonitrile, relative to the carbon-carbon double bonds in the
allyl ether compound of the raw material, the reaction liquid can
easily become a homogeneous phase, which is preferable. Further, if
the amount of nitrile groups in acetonitrile is 2 molar equivalent
or more, the percent yield is preferable, and if the amount is 15
molar equivalent or less, the epoxidation selectivity of the
hydrogen peroxide, and the cost are preferable.
[0040] Acetonitrile can be additionally supplied during the
reaction. When acetonitrile is added, the ratio of the total amount
of acetonitrile relative to the total amount of the allyl ether
compound of the raw material (acetonitrile/carbon-carbon double
bonds in allyl ether compound of the raw material (molar ratio))
should be in the above range, namely, preferably 2.0 to 15, more
preferably 3.0 to 10, and still more preferably 4.0 to 8.0.
[0041] When an epoxidation reaction is performed under the presence
of acetonitrile, preferably, a proton-donor solvent is coexisted in
the reaction liquid, and the hydrogen peroxide acts on the allyl
ether compound of the raw material, under the presence of the
proton-donor solvent. The proton-donor solvent functions as a
solvent for the allyl ether compound of the raw material. When the
allyl ether compound of the raw material has a high viscosity, the
proton-donor solvent also functions as a viscosity depressant to
increase the moving speed of the hydrogen peroxide toward the allyl
ether compound of the raw material.
[0042] Specific examples of the proton-donor solvent may include
alcohol, amine, thiol, etc. These proton-donor solvents may be used
in combination. Among them, alcohol is preferable, particularly
when the allyl ether compound of the raw material has low
hydrophilicity, because alcohol has a function to suppress the
separation of the organic phase including the allyl ether compound
of the raw material and acetonitrile, and the aqueous phase
including the hydrogen peroxide, so as to make the reaction liquid
to a homogeneous phase and increase the reaction rate. Among
alcohols, an alcohol having 1 to 4 carbon atoms is preferable, a
primary alcohol having 1 to 4 carbon atoms is more preferably, and
methanol, ethanol, and 1-propanol are still more preferable.
[0043] Usage of the proton-donor solvent, relative to 100 parts by
mass of the allyl ether compound of the raw material, is preferably
10 to 1000 parts by mass, more preferably 80 to 800 parts by mass,
and still more preferably 100 to 500 parts by mass. Usage of the
proton-donor solvent varies depending on the structure of the allyl
ether compound of the raw material, and thus, cannot be generally
determined. However, using 10 to 1000 parts by mass of the
proton-donor solvent relative to 100 parts by mass of the allyl
ether compound of the raw material, is preferable, because the
reaction liquid can easily be a homogeneous phase. Further, if the
usage of the proton-donor solvent is 10 parts by mass or more and
1000 parts by mass or less, relative to 100 parts by mass of the
allyl ether compound of the raw material, the reaction rate is
preferable.
[0044] Usage of the proton-donor solvent, relative to 100 parts by
mass of acetonitrile is preferably 20 to 500 parts by mass, more
preferably 25 to 400 parts by mass, and still more preferably 33 to
300 parts by mass. When the allyl ether compound of the raw
material has higher hydrophobicity, and has higher solubility to an
organic solvent such as acetonitrile, increasing the ratio of
acetonitrile is preferable. Namely, performing the reaction, while
the usage of the proton-donor solvent is made closer to 20 parts by
mass, relative to 100 parts by mass of acetonitrile, is
preferable.
[0045] The reaction liquid containing the allyl ether compound of
the raw material, has a pH, at any selected point, of preferably 8
to 12, more preferably 9 to 11, and still more preferably 9.5 to
11. If the pH is 8 or more, the reaction rate is preferable, and
high productivity can be maintained. If the pH is 12 or less,
sufficient safety can be secured during the reaction and a
sufficient percent yield can be obtained. Since hydrogen peroxide
actively decomposes under a high-alkaline atmosphere, controlling
the pH of the reaction liquid to around 9 to 10 at the initial
stage of the reaction, and then, controlling the pH to around 10 to
11 by gradually increasing the pH along with the addition of the
hydrogen peroxide, in accordance with needs, is more
preferable.
[0046] In order to adjust the pH of the reaction liquid, an
alkaline compound may be used, so that the hydrogen peroxide acts
on the allyl ether compound of the raw material, under the presence
of the alkaline compound. Examples of the alkaline compound which
can be used for adjusting the pH of the reaction liquid may include
salts of inorganic bases such as potassium carbonate, potassium
hydrogen carbonate, potassium hydroxide, sodium hydroxide, cesium
hydroxide, etc., and salts of organic bases such as potassium
methoxide, potassium ethoxide, sodium methoxide, sodium ethoxide,
tetramethylammonium hydroxide, etc. Among them, potassium
carbonate, potassium hydrogen carbonate, potassium hydroxide,
sodium hydroxide, potassium methoxide, potassium ethoxide, sodium
methoxide, and sodium ethoxide are preferable because the pH
adjustment is easy. Further, potassium hydroxide and sodium
hydroxide are more preferable because they have high solubility to
water and alcohol, and superior reactivity.
[0047] The alkaline compound may be used by dissolving the alkaline
compound in water or in a solution of a proton-donor solvent, and
using the alkaline compound in such a way is preferable. A
preferable proton-donor solvent is alcohol, such as methanol,
ethanol, propanol, butanol, etc. Using a proton-donor solvent same
as the above-mentioned proton-donor solvent is preferable.
Preferably, the solution of the alkaline compound should be added
so that the reaction liquid maintains its pH 9 more, even if the
hydrogen peroxide is added.
[0048] The order and the state of adding the allyl ether compound
of the raw material, hydrogen peroxide, acetonitrile, the
proton-donor solvent, and the alkaline compound, to the reaction
system are not particularly limited. However, in view of the
stability in industrial production, preferably, the allyl ether
compound of the raw material, acetonitrile, and the proton-donor
solvent are supplied to a reactor first, the reaction temperature
is maintained as much as possible, and the hydrogen peroxide
aqueous solution is gradually added while confirming that hydrogen
peroxide is consumed in the reaction. This is preferable because
the epoxidation reaction can be accelerated, and a reaction product
can be easily separated and purified. According to this method,
even if abnormal decomposition of the hydrogen peroxide occurs and
oxygen gas is generated in the reactor, since the accumulated
amount of the hydrogen peroxide in the reactor is small, the
increase of pressure can be suppressed to the lowest level.
[0049] The reaction is performed in the homogeneous phase. When the
reaction liquid is in the homogeneous phase, the allyl ether
compound of the raw material can be efficiently reacted with
hydrogen peroxide and acetonitrile which are required for
epoxidation, without the phase transfer. Therefore, less unreacted
materials remains after the reaction, and the objective epoxide can
be produced at a high percent yield. The ratio of the components
required for making the reaction liquid to a homogeneous phase may
change depending on the structure of the allyl ether compound of
the raw material, and thus, cannot be determined. However, as
mentioned above, the ratio can be adjusted by appropriately
changing the amounts of acetonitrile and/or the proton-donor
solvent.
[0050] As mentioned above, the reaction liquid preferably has a pH
of 8 to 12, at any selected point. The timing for adding the
alkaline compound which is an optional component for adjusting the
pH of the liquid, is not limited. A predetermined amount of the
alkaline compound may be initially supplied to the reactor. In this
case, addition during the reaction is not always necessary. The
alkaline compound may not be supplied initially, and may be only
added during the reaction. Since hydrogen peroxide actively
decomposes under a high-alkaline atmosphere, controlling the pH to
around 9 to 10 at the initial stage of the reaction, and then,
controlling the pH to around 10 to 11 by gradually increasing the
pH along with the addition of the hydrogen peroxide, in accordance
with needs, is more preferable.
[0051] The reaction temperature is preferably 0.degree. C. to
60.degree. C., more preferably 10.degree. C. to 50.degree. C., and
still more preferably 20.degree. C. to 40.degree. C. If the
reaction temperature is 0.degree. C. or higher, the reaction
progresses favorably, and if the reaction temperature is 60.degree.
C. or lower, volatilization or boiling of acetonitrile and the
proton-donor solvent can be suppressed.
[0052] The reaction time depends on the reaction temperature, and
cannot be determined unconditionally, but is normally 2 to 100
hours, preferably 4 to 80 hours, and more preferably 6 to 60
hours.
[0053] After the reaction is complete, an organic phase containing
the reaction product is collected and condensed to obtain a crude
reaction product. The reaction liquid normally contains hydrogen
peroxide. Thus, in case that the organic phase containing the
reaction product is collected after the moisture in the reaction
liquid is removed, removing the hydrogen peroxide by reduction in
advance is preferable, in order to avoid the risk of explosion due
to the condensation of the hydrogen peroxide. The reducing agent
used for the removal by reduction may be sodium sulfite, sodium
thiosulfate, etc., but is not limited thereto. Further, when the
organic phase containing the reaction product is collected, in
order to efficiently separating and removing the moisture in the
reaction liquid, from the organic phase containing the reaction
product, adding an appropriate amount of an organic solvent having
low compatibility with water to the reaction liquid, is preferable.
Examples of the organic solvent may include toluene, ethyl acetate,
dichloromethane, etc., but are not limited to these organic
solvents. According to these processes, hydrogen peroxide remaining
in the reaction liquid may be removed, and the aqueous phase can be
separated from the organic phase containing the organic
solvent.
[0054] As mentioned above, the organic phase is separated from the
aqueous phase, condensed, and then, subjected to an ordinary method
such as distillation, separation with chromatography,
recrystallization, sublimation, etc. Thus, the generated epoxide of
the allyl ether compound of the raw material, can be extracted.
[0055] When the eugenol-derived epoxide produced as above is
reacted with a (meth)acrylic acid (Formula (7)), eugenol-derived
epoxy (meth)acrylate, which is an epoxy (meth)acrylate compound
according to an aspect, can be produced.
##STR00013##
[0056] (wherein, R.sup.8 represents a hydrogen atom or a methyl
group).
[0057] Also, when the above-mentioned 2-allylphenol-derived epoxide
is reacted with a (meth) acrylic acid (Formula (8)),
2-allylphenol-derived epoxy (meth)acrylate, which is an epoxy
(meth)acrylate compound according to an aspect, can be
produced.
##STR00014##
[0058] (wherein, R.sup.9 represents a hydrogen atom or a methyl
group).
[0059] When a (meth) acrylic acid is added to an epoxide, reaction
can be performed without a solvent, or by using a solvent. The
solvent is not limited, as far as the solvent does not inhibit the
reaction. Examples of the solvent can include an ester-based
solvent such as propyleneglycol monomethyl ether acetate,
diethyleneglycol monoethyl ether acetate, etc. Examples of the
catalyst for the reaction between the epoxide and the (meth)
acrylic acid can include a phosphine-based catalyst such as
triphenylphosphine, tributylphosphine, etc., a tertiary amine-based
catalyst such as diazabicycloundecene, etc., and an imidazole-based
catalyst such as ethylimidazole, etc. Further, in order to prevent
polymerization of (meth)acryloyl groups during the reaction, a
polymerization inhibitor such as hydroquinone, hydroquinone
monomethyl ether, phenothiazine, 2,6-di-t-butyl-p-cresol, etc., can
be used.
[0060] The conditions for the reaction between the epoxide and the
(meth) acrylic acid may include a reaction temperature of
20.degree. C. to 180.degree. C., preferably 50.degree. C. to
150.degree. C., and more preferably 60.degree. C. to 130.degree.
C., and a reaction time of 1 to 24 hours. The reaction is ended
when the acid value becomes 5 or less. The addition amount of the
(meth) acrylic acid relative to the epoxide, in terms of the epoxy
group in the epoxide, is preferably 1 to 2 equivalents, and more
preferably 1 to 1.5 equivalents. The reaction may progress without
a reaction catalyst. However, when a reaction catalyst is used, the
usage of the reaction catalyst is preferably 0.1 to 2 parts by
mass, relative to 100 parts by mass of the (meth) acrylic acid.
When a polymerization inhibitor is used, the usage of the
polymerization inhibitor is preferably 0.01 to 1 parts by mass,
relative to 100 parts by mass of the (meth) acrylic acid.
Curable Composition
[0061] A curable composition according to an aspect comprises the
above-mentioned epoxy (meth)acrylate compound, a
photopolymerization initiator, and at least one of monomers and
oligomers having a (meth)acryloyl group. The photopolymerization
initiator is not limited, but a photo-radical initiator is
preferable from a viewpoint of high reactivity to ultraviolet rays.
Examples of the photo-radical initiator may include acetophenone,
propiophenone, benzophenone, xanthol, fluorene, benzaldehyde,
anthraquinone, triphenylamine, carbazole, 3-methylacetophenone,
4-methylacetophenone, 3-pentylacetophenone,
2,2-diethoxyacetophenone, 4-methoxyacetophenone,
3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene,
3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone,
4,4'-dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone,
3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone,
benzoin, benzoin methyl ether, benzoin butyl ether,
bis(4-dimethylaminophenyl)ketone, benzyl methoxy ketal, 2-chloro
thioxanthone, 2,2-dimethoxy-1,2-diphenylethan-1-one (IRGACURE
(registered trademark) 651, manufactured by BASF Japan Ltd.),
1-hydroxy-cyclohexyl-phenyl ketone (IRGACURE (registered trademark)
184, manufactured by BASF Japan Ltd.), 2-hydroxy-2-methyl-1-phenyl
propan 1-one (DAROCUR (registered trademark) 1173, manufactured by
BASF Japan Ltd.),
1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan 1-one
(IRGACURE (registered trademark) 2959, manufactured by BASF Japan
Ltd.), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one
(IRGACURE (registered trademark) 907, manufactured by BASF Japan
Ltd.), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1
(IRGACURE (registered trademark) 369, manufactured by BASF Japan
Ltd.),
2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholin-4-yl-phenyl)-butan-1-on-
e (IRGACURE (registered trademark) 379, manufactured by BASF Japan
Ltd.), dibenzoyl, and the like.
[0062] Among them, .alpha.-hydroxy ketone compounds (for example,
benzoin, benzoin methyl ether, benzoin butyl ether,
1-hydroxy-cyclohexyl phenyl ketone, etc.), and phenyl ketone
derivatives (for example, acetophenone, propiophenone,
benzophenone, 3-methylacetophenone, 4-methylacetophenone,
3-pentylacetophenone, 2,2-diethoxyacetophenone,
4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone,
3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone,
4,4'-dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone,
bis(4-dimethylaminophenyl)ketone, etc.), are preferable.
[0063] When each of the above epoxy (meth)acrylate compounds
obtained according to the above-mentioned methods is contained in
an epoxy (meth)acrylate composition which is used for a protective
film of a conductive pattern, occurrence of migration can be
suppressed. The composition may be a mixture of each epoxy
(meth)acrylate compound, a monomer or an oligomer having a
(meth)acryloyl group, and a photopolymerization initiator. The
mixing ratio in the composition varies depending on the forming
methods of the protective film of the composition, but can be 20 to
90 parts by mass of the epoxy (meth)acrylate compound; 10 to 80
parts by mass of the monomer or the oligomer having a
(meth)acryloyl group; and 1 to 5 parts by mass of a
photopolymerization initiator relative to 100 parts by mass of the
total of the epoxy (meth)acrylate compound and the monomer or the
oligomer having a (meth)acryloyl group.
[0064] Examples of the monomer or oligomer having a (meth)acryloyl
group may include trimethylol propane triacrylate, neopentyl glycol
polypropoxy diacrylate, neopentyl glycol diacrylate,
trimethylolpropane polyethoxy triacrylate, bisphenol F polyethoxy
diacrylate, bisphenol A polyethoxy diacrylate, dipentaerythritol
polyhexanolide hexaacrylate, tris(hydroxyethyl)isocyanurate
polyhexanolide triacrylate, tricyclodecane dimethylol diacrylate,
2-(2-acryloyloxy-1,1-dimethyl)-5-ethyl-5-acryloyloxymethyl-1,3-dioxane,
tetrabromo bisphenol A diethoxydiacrylate, 4,4-dimercapto diphenyl
sulfide dimethacrylate, poly tetraethylene glycol diacrylate,
1,9-nonanediol diacrylate, 1,6-hexanediol diacrylate, dimethylol
tricyclodecane diacrylate, ditrimethylol propane tetraacrylate,
tetramethylol methane tetraacrylate, pentaerythritol triacrylate,
pentaerythritol tetraacrylate, dipentaerythritol monohydroxy
pentaacrylate, dipentaerythritol hexaacrylate, 1,4-butylene glycol
diacrylate, polyethylene glycol diacrylate, commercially offered
oligoester acrylate, aromatic-, aliphatic-, etc., urethane acrylate
(oligomer), and the like.
[0065] Further, the above composition may include a solvent.
Examples of this solvent are solvents which can be used for
synthesizing the above-mentioned epoxy (meth)acrylate compound.
[0066] Further, if the epoxide used as a raw material at the
production stage is a halogen-free epoxide as mentioned above, the
amount of halogen contained, as impurities, in the produced epoxy
(meth)acrylate compound, can be largely reduced. Therefore, the
epoxy (meth)acrylate compound has a halogen atom content of 100 ppm
by mass or less, and preferably 50 mass ppm or less, more
preferably 30 mass ppm or less, and still more preferably 15 mass
ppm.
EXAMPLES
[0067] Hereinafter, specific examples of the present disclosure
will be explained. The examples are described below for the purpose
of easy understanding of the present disclosure, and the present
disclosure is not limited to these examples.
<Acid Value Measurement Method>
[0068] In the present Examples, acid values are values measured by
the following method.
[0069] Approximately 0.2 g of a sample was precisely weighed, by a
precision balance, into a 100 mL conical flask, and 10 mL of
mixture solvent having ethanol/toluene=1/2 (mass ratio) was added
thereto to dissolve the sample. Further, 1 to 3 drops of
phenolphthalein ethanol solution were added to the container as an
indicator, which was sufficiently stirred until the sample was
uniformly mixed. The mixture was subjected to titration with a 0.1
N potassium hydroxide-ethanol solution, and the end of
neutralization was determined by the fact that the slight red color
of the indicator continues for 30 seconds. The value obtained from
the result, using the following calculation formula, was determined
as an acid value of the sample.
Acid Value(mgKOH/g)=[B.times.f.times.5.611]/S
B: Use quantity of 0.1 N potassium hydroxide-ethanol solution (mL)
f: Factor of 0.1 N potassium hydroxide-ethanol solution S:
Collection quantity of sample (g)
<Viscosity Measurement Method>
[0070] In the present Examples, viscosities are values measured by
the following method.
[0071] Using a B-type viscometer DV-II+Pro, manufactured by
Brookfield Engineering, the viscosity of a sample was measured at
25.degree. C. When the viscosity exceeds 10000 mPas, Rotor No. 52
was used for measurement, and when the viscosity is 10000 mPas or
less, Rotor No. 40 was used for measurement, respectively.
<Epoxy Equivalent Measurement Method>
[0072] Epoxy equivalents were measured according to JIS
K7236:2001.
Raw Material Synthesis Example 1
Synthesis of Substrate (2-Allylphenol Allyl Ether)
[0073] A solution prepared by dissolving 567 g (4.10 mol) of
potassium carbonate (manufactured by Nippon Soda, Co., Ltd.) in 750
g of pure water, and 500 g (3.73 mol) of 2-allylphenol
(manufactured by Tokyo Chemical Industry, Co., Ltd.) represented by
Formula (9) were added in a 3 L three-neck round-bottom flask, and
the reactor was subjected to nitrogen gas replacement and heated to
85.degree. C. Under a nitrogen stream, 448 g (4.47 mol) of allyl
acetate (manufactured by Showa Denko K.K.), 9.77 g (37.3 mmol) of
triphenylphosphine (manufactured by Hokko Chemical Industry Co.,
Ltd.), and 3.17 g (0.750 mmol (in terms of Pd atom)) of 50%
wetted-with-water 5%-Pd/C-STD type (manufactured by N.E. Chemcat
Corporation) were added in the reactor, and under a nitrogen gas
atmosphere, the temperature of the reactor was raised to
105.degree. C. to continue the reaction for four hours. Thereafter,
44.8 g (0.447 mol) of allyl acetate was further added, and the
resultant was continued to be heated for 12 hours. After the
reaction was complete, the reaction system was cooled to a room
temperature, and then, pure water was added thereto until all of
the precipitated salt was dissolved, and the resultant was
subjected to a separation treatment. The organic phase was
separated, and the organic solvent (70.degree. C., 50 mmHg, 2
hours) was distilled away. Pure water (500 g) was added, and
thereafter, 500 g of toluene was added, which was maintained at a
temperature of 80.degree. C. or higher. After confirmation that no
white precipitate appeared, Pd/C was filtered (using a 1 micron
membrane filter KST-142-JA (manufactured by Advantech Co., Ltd.),
while applying pressure (0.3 MPa)) and collected. The filter cake
was washed with 100 g of toluene, and the aqueous phase was
separated. The organic phase was washed twice, with 500 g of pure
water, at 50.degree. C. or higher, and the aqueous phase was
confirmed as neutral. The organic phase was separated, and
thereafter, condensed under reduced pressure, to thereby obtain a
pale yellow liquid (669 g, 3.66 mol, 98.0% percent yield) mainly
composed of an allyl ether compound of 2-allylphenol represented by
Formula (10). According to the .sup.1H-NMR measurement of the pale
yellow liquid, the compound represented by Formula (10) was
contained as a main component. The measurement data attributed to
the compound represented by Formula (10) is shown below.
[0074] .sup.1H-NMR {400 MHz, CDCl.sub.3, 27.degree. C.},
.delta.3.32 (2H, dt, PhCH.sub.2CH.dbd.CH.sub.2), .delta.4.54 (2H,
dt, PhOCH.sub.2CH.dbd.CH.sub.2), .delta.5.01-5.09 (2H, m,
PhCH.sub.2CH.dbd.CH.sub.2), .delta.5.27 (1H, dq,
PhOCH.sub.2CH.dbd.CHH), .delta.5.42 (1H, dq,
PhOCH.sub.2CH.dbd.CHH), .delta.5.95 (1H, m,
PhCH.sub.2CH.dbd.CH.sub.2), .delta.6.06 (1H, m,
PhOCH.sub.2CH.dbd.CH.sub.2), .delta.6.92 (m, 2H, aromatic),
.delta.7.09 (2H, m, aromatic).
##STR00015##
Raw Material Synthesis Example 2
Synthesis of Substrate (Eugenol Allyl Ether)
[0075] The reaction was performed under the same conditions as the
Raw Material Synthesis Example 1, except that 2-allylphenol was
changed to eugenol. The amounts of substance of the reagents used
in the reaction, and the physical property data of the obtained
allyl ether, are shown below.
[0076] A solution prepared by dissolving 463 g (3.35 mol) of
potassium carbonate (manufactured by Nippon Soda, Co., Ltd.) in 750
g of pure water, and 500 g (3.04 mol) of eugenol (manufactured by
Tokyo Chemical Industry, Co., Ltd.) represented by Formula (11)
were added in a 3 L three-neck round-bottom flask, and the reactor
was subjected to nitrogen gas replacement and heated to 85.degree.
C. Under a nitrogen stream, 366 g (3.65 mol) of allyl acetate
(manufactured by Showa Denko K.K.), 8.00 g (30.5 mmol) of
triphenylphosphine (manufactured by Hokko Chemical Industry Co.,
Ltd.), and 2.59 g (0.610 mmol (in terms of Pd atom)) of 50% wetted
5%-Pd/C-STD type (manufactured by N.E. Chemcat Corporation) were
added in the reactor, and under a nitrogen gas atmosphere, the
temperature of the reactor was raised to 105.degree. C. to continue
the reaction for four hours. Thereafter, 36.6 g (0.365 mol) of
allyl acetate was further added, which was continued to be heated
for 12 hours. After the reaction was complete, the reaction system
was cooled to a room temperature, and then, pure water was added
thereto until all of the precipitated salt was dissolved, and the
resultant was subjected to a separation treatment. The organic
phase was separated, and the organic solvent (70.degree. C., 50
mmHg, 2 hours) was distilled away. Pure water (500 g) was added,
and thereafter, 500 g of toluene was added, which was maintained at
a temperature of 80.degree. C. or higher. After confirmation that
no white precipitate appeared, Pd/C was filtered (using a 1 micron
membrane filter KST-142-JA (manufactured by Advantech Co., Ltd.),
while applying pressure (0.3 MPa)) and collected. The filter cake
was washed with 100 g of toluene, and the aqueous phase was
separated. The organic phase was washed twice, with 500 g of pure
water, at 50.degree. C. or higher, and the aqueous phase was
confirmed as neutral. The organic phase was separated, and
thereafter, condensed under reduced pressure, to thereby obtain a
pale yellow liquid (611 g, 2.99 mol, 98.5% percent yield) mainly
composed of an allyl ether compound of eugenol represented by
Formula (12).
##STR00016##
Synthesis Example 1
Synthesis of Eugenol-Derived Epoxide
[0077] 300 g (1.47 mol) of the allyl ether compound of eugenol
obtained by the above-mentioned Raw Material Synthesis Example 2,
707 g (17.2 mol) of acetonitrile (manufactured by Junsei Chemical
Co., Ltd.), and 1240 g (38.6 mol) of methanol (manufactured by
Junsei Chemical Co., Ltd.) were added in a 5 L three-neck flask,
and a small amount of 50%-by-mass potassium hydroxide aqueous
solution (manufactured by Wako Pure Chemical Corporation) was added
thereto to adjust the pH of the resultant reaction liquid to
approximately 10.5. Thereafter, 1040 g (9.18 mol) of 30%-by-mass
hydrogen peroxide aqueous solution (manufactured by Mitsubishi Gas
Chemical Company Inc.) was dropped at an inner temperature of
35.degree. C. The dropping took 18 hours, and during the dropping,
the inner temperature was kept so as not to exceed 45.degree. C.
The addition of the hydrogen peroxide aqueous solution resulted in
lowering the pH. Thus, a 50%-by-mass potassium hydroxide aqueous
solution was also added in order to keep the pH to 9.0 to 11. After
the reaction, 500 g of 10% sodium sulfite aqueous solution
(prepared by dissolving sodium sulfite, manufactured by Wako Pure
Chemical Corporation, in pure water), and 750 g of toluene were
added, which was stirred for 30 minutes at a room temperature. The
aqueous phase was separated, and thereafter, the organic phase was
washed twice with 500 g of pure water, to distill the solvent away.
Thereby, a reaction product (objective product) was obtained. The
obtained eugenol-derived epoxide (EUGG) had an epoxy equivalent of
122 g/eq. FIG. 1 shows a result of the .sup.1H-NMR measurement of
the obtained product. According to FIG. 1, it was confirmed that a
compound represented by Formula (13) was contained as a main
component.
##STR00017##
Synthesis Example 2
Synthesis of 2-Allylphenol-Derived Epoxide
[0078] 300 g (1.72 mol) of the allyl ether compound of
2-allylphenol obtained by the above-mentioned Raw Material
Synthesis Example 1, 980 g (23.9 mol) of acetonitrile (manufactured
by Junsei Chemical Co., Ltd.), and 330 g (10.3 mol) of methanol
(manufactured by Junsei Chemical Co., Ltd.) were added in a 5 L
three-neck flask, and a small amount of 50%-by-mass potassium
hydroxide aqueous solution (manufactured by Wako Pure Chemical
Corporation) was added thereto to adjust the pH of the resultant
reaction liquid to approximately 10.5. Thereafter, 1170 g (10.3
mol) of 30%-by-mass hydrogen peroxide aqueous solution
(manufactured by Mitsubishi Gas Chemical Company Inc.) was dropped
at an inner temperature of 35.degree. C. The dropping took 18
hours, and during the dropping, the inner temperature was kept so
as not to exceed 45.degree. C. The addition of the hydrogen
peroxide aqueous solution resulted in lowering the pH. Thus, a
50%-by-mass potassium hydroxide aqueous solution was also added in
order to keep the pH to 9.0 to 11. After the reaction, 500 g of
10%-by-mass sodium sulfite aqueous solution (prepared by dissolving
sodium sulfite, manufactured by Wako Pure Chemical Corporation, in
pure water), and 750 g of toluene were added, which was stirred for
30 minutes at a room temperature. The aqueous phase was separated,
and thereafter, the organic phase (toluene) was washed twice with
500 g of pure water, to distill the solvent away. Thereby, a
reaction product (objective product) was obtained. The obtained
2-allylphenol-derived epoxide (2APG) had an epoxy equivalent of 112
g/eq. FIG. 2 shows a result of the .sup.1H-NMR measurement of the
obtained product. According to FIG. 2, it was confirmed that a
compound represented by Formula (14) was contained as a main
component.
##STR00018##
Synthesis Example 3
Synthesis of Eugenol-Derived Epoxide
[0079] According to Polym Int 2014; 63: 760-765, EUGG was
synthesized.
Synthesis Example 4
Synthesis of 2-Allylphenol-Derived Epoxide
[0080] According to U.S. Pat. No. 2,965,607, 2APG was
synthesized.
Example 1
Synthesis of Eugenol-Derived Epoxy Acrylate (EUGG Acrylate)
[0081] 50.1 g (epoxy group considering epoxy equivalent: 0.205 mol)
of eugenol-derived epoxide (EUGG) synthesized by Synthesis Example
1, 0.016 g of phenothiazine (manufactured by Wako Pure Chemical
Corporation), and 0.264 g of triphenylphosphine (manufactured by
Hokko Chemical Industry Co., Ltd.) were added in a flask, and
stirred at 70.degree. C. Then, 29.8 g (0.414 mol) of acrylic acid
(manufactured by Showa Denko K.K.) was slowly dropped thereto.
After the dropping, the temperature was raised to 120.degree. C.,
and stirred. Sampling was performed at appropriate times and the
acid values were measured. When 4 hours passed, the acid value
became 5 or less, and at that time, the reaction was ended. The
actual yield was 72.5 g, the percent yield was 93.0%, the acid
value was 2.3, and the viscosity was 139000 Pa-s.
[0082] The obtained compound was identified by .sup.1H-NMR. FIG. 3
shows the above-mentioned .sup.1H-NMR spectrum. In FIG. 3, the
peaks around 3.2 ppm and 2.6 ppm derived from epoxy groups and
shown in FIG. 1, disappear; and new peaks around 5.9 ppm to 6.4 ppm
derived from acryloyl groups are found. Thereby, the synthesis of
EUGG acrylate represented by Formula (15) can be confirmed.
##STR00019##
[0083] Further, signals in the .sup.1H-NMR spectrum of the obtained
EUGG acrylate are as follows:
[0084] 7.3 ppm (s, 1H), 6.9 ppm (t, 1H), 6.8 ppm (s, 1H), 6.4 ppm
(m, 2H), 6.2 ppm (m, 2H), 5.9 ppm (m, 2H), 4.5 ppm (q, H), 4.3 ppm
(m, 2H), 4.1 ppm (m, 2H), 3.8 ppm (s, 3H), 2.9 ppm (d, H), 2.8 ppm
(m, 2H).
Example 2
Synthesis of 2-Allylphenol-Derived Epoxy Acrylate (2APG
Acrylate)
[0085] 50.0 g (epoxy group considering epoxy equivalent: 0.223 mol)
of 2-allylphenol-derived epoxide (2APG) synthesized by Synthesis
Example 2, 0.016 g of phenothiazine (manufactured by Wako Pure
Chemical Corporation), and 0.260 g g of triphenylphosphine
(manufactured by Hokko Chemical Industry Co., Ltd.) were added in a
flask, and stirred at 70.degree. C. Then, 32.6 g (0.452 mol) of
acrylic acid (manufactured by Showa Denko K.K.) was slowly dropped
thereto. After the dropping, the temperature was raised to
120.degree. C., and stirred. Sampling was performed at appropriate
times and the acid values were measured. When 5 hours passed, the
acid value became 5 or less, and at that time, the reaction was
ended. The actual yield was 73.0 g, the percent yield was 93.4%,
the acid value was 3.7, and the viscosity was 125000 mPas.
[0086] The obtained compound was identified by .sup.1H-NMR. FIG. 4
shows the above-mentioned .sup.1H-NMR spectrum. In FIG. 4, the
peaks around 3.2 ppm and 2.6 ppm derived from epoxy groups and
shown in FIG. 2, disappear; and new peaks around 5.9 ppm to 6.5 ppm
derived from acryloyl groups are found. Thereby, the synthesis of
2APG acrylate represented by Formula (16) can be confirmed.
##STR00020##
[0087] Further, signals in the .sup.1H-NMR spectrum of the obtained
2APG acrylate are as follows:
[0088] 7.5 ppm (t, 1H), 7.3 ppm (s, 1H), 7.2 ppm (m, 1H), 6.9 ppm
(dq, 1H), 6.5 ppm (q, 2H), 6.2 ppm (q, 2H), 5.9 ppm (t, 2H), 4.4
ppm (m, 2H) 4.1 ppm (m, 2H), 3.6 ppm (m, H), 2.9 ppm (m, 1H), 2.8
ppm (m, 2H).
Comparative Example 1
[0089] Instead of the EUGG synthesized by Synthesis Example 1, the
same mass of the EUGG synthesized by Synthesis Example 3 was used.
Others were the same as those of Example 1.
Comparative Example 2
[0090] Instead of the 2APG synthesized by Synthesis Example 2, the
same mass of the 2APG synthesized by Synthesis Example 4 was used.
Others were the same as those of Example 2.
<Total Chlorine Amount Measurement>
[0091] According to JIS K-7243-3, the total amounts of chlorine in
the epoxy acrylate compounds of Examples 1 and 2 and Comparative
Examples 1 and 2, were measured, respectively. Table 1 shows the
results.
TABLE-US-00001 TABLE 1 Total Chlorine Total Chlorine Amount/Mass
ppm Amount/Mass ppm Example 1 10.4 Comparative 2534 Example 1
Example 2 8.1 Comparative 1356 Example 2
[0092] From Table 1, it is apparent that Examples 1 and 2 using
epoxy acrylate compounds according to Synthesis Examples 1 and 2
show lower chlorine amounts, compared to Comparative Examples 1 and
2 using epoxy acrylate compounds according to Synthesis Examples 3
and 4.
<Reliability Test>
[0093] 27 parts by mass of commercially offered polyfunctional
polyester acrylate (M-7100, manufactured by Toagosei Co., Ltd.),
and 3 parts by mass of IRGACURE (registered trademark) 184 as a
photoinitiator, were added to 70 parts by mass of each of the epoxy
acrylate compounds according to Examples 1 and 2 and Comparative
Examples 1 and 2, and mixed to become homogeneous. Each of the
obtained curable compositions was printed, by a bar coater, to have
a thickness of appropriately 5 .mu.m, on a comb-shaped pattern of a
comb-shaped test piece for measurement defined by ISO 9455-17.
Using a small UV irradiation device QRU-2161-Z11-00 (Orc
Manufacturing Co., Ltd.), the test pieces were exposed to UV at
approximately 40 mW/cm.sup.2, and cured test pieces were
produced.
[0094] Ten test pieces were made from each curable composition, and
the test pieces were stored in a constant-temperature
constant-humidity chamber at 85.degree. C. and 85 RH %. After 1000
hours, with the applied voltage of 100 V, if the inter-electrode
insulation resistance of a test piece became 1/1000 or less of the
initial resistance value (the order of the 11.sup.th power of 10),
it was determined that migration occurred in the test piece. The
number of such test pieces were counted. Table 2 shows the results.
In Table 2, the number of test pieces in which migration occurred,
are described.
TABLE-US-00002 TABLE 2 Reliability Test Reliability Test Example 1
0 Comparative 7 Example 1 Example 2 0 Comparative 8 Example 2
[0095] As shown in Table 2, with respect to the epoxy acrylate
compositions using the epoxy acrylate compounds according to
Examples 1 and 2, no occurrence of migration was found. On the
other hand, with respect to the epoxy acrylate compositions using
the epoxy acrylate compounds according to Comparative Examples 1
and 2, migration occurred at a high rate. The reason therefor is
believed that the ratio of halogen (chlorine) contained in the
epoxy acrylate compound according to each Comparative Example is
extremely higher than that of each Example.
* * * * *